Hydrochloric Acid → HCID 54090446, compound

HRID 1029522Notes

Reaction equation

HRID 1029522 reaction equation
[C:1](Cl)(Cl)=[S:2].[CH3:5][C:6]([C:9]1[CH:14]=[C:13]([SH:15])[CH:12]=[C:11]([C:16]([CH3:19])([CH3:18])[CH3:17])[C:10]=1[OH:20])([CH3:8])[CH3:7].C(N(CC)C(C)C)(C)C.Cl.O.[NH2:32][NH2:33]>C1(C)C=CC=CC=1.ClCCl.ClCCl.C(OCC)(=O)C.O>[NH:32]([C:1]([S:15][C:13]1[CH:12]=[C:11]([C:16]([CH3:19])([CH3:18])[CH3:17])[C:10]([OH:20])=[C:9]([C:6]([CH3:5])([CH3:7])[CH3:8])[CH:14]=1)=[S:2])[NH2:33]

Participants

10

Reactant 5

HCID 313Hydrochloric AcidHCID 10040ThiophosgeneHCID 24654Hydrazine hydrate (1:1)HCID 703702,6-Di-tert-butyl-4-mercaptophenolHCID 81531Diisopropylethylamine

Product 1

HCID 54090446HCID 54090446, compoundYield 53.3%

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent2×HCID 21877217Toluene methylene chlorideSolvent

Conditions

Temperature
0 °C

Procedure

Thiophosgene (1.6 mL, 21.0 mmol) is added dropwise to a -78° C. solution of 2,6-bis(1,1-dimethylethyl)-4-mercaptophenol (5.0 g, 21.0 mmol) and N,N-diisopropylethylamine (5.4 mL, 31.4 mmol) in toluene/dichloromethane (100 mL/20 mL). The reaction mixture is stirred for 1.5 hours then poured into a separatory funnel containing ethyl acetate and water. The aqueous phase is acidified to pH 3 with 1N hydrochloric acid. The organic phase is washed twice with water, then with a saturated solution of sodium bicarbonate followed by brine. Drying the organic phase over magnesium sulfate and evaporation of the solvents gives a crude product which is dissolved in dichloromethane (200 mL) and cooled to 0° C. Hydrazine monohydrate (1.5 mL, 31.0 mmol) is added in three portions at 30 minute intervals, and the solution is stirred for 1 hour. The reaction is poured into ethyl acetate and washed four times with an aqueous solution of sodium chloride and once with a saturated solution of sodium chloride. Drying the organic phase over magnesium sulfate and evaporation gives an amorphous solid which is crystallized from 50 mL of ethyl acetate/hexane (5/95) affording 3.5 g (53% from 2,6-bis(1,1-dimethylethyl)-4-mercaptophenol) of 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl hydrazinecarbodithioate, mp 145.5°-146.0° C.

Workup

  1. additionthen poured into a separatory funnel
  2. washThe organic phase is washed twice with water
  3. customDrying the organic phase
  4. customover magnesium sulfate and evaporation of the solvents
  5. customgives a crude product which
  6. stirringthe solution is stirred for 1 hour
  7. washwashed four times with an aqueous solution of sodium chloride
  8. customDrying the organic phase
  9. customover magnesium sulfate and evaporation
  10. customgives an amorphous solid which
  11. customis crystallized from 50 mL of ethyl acetate/hexane (5/95)

Sources & evidence

ORD record
ord-3084364e686b46d0abae385aa1f61c06
Source dataset
uspto-grants-1992_04
Patent number
US05102897

Reaction notes

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